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    • 专利摘要:
    A diesel fuel additive composition, a fuel containing the fuel additive, a method of improving the performance of a diesel engine by using the additive. The diesel fuel additive comprises a reaction product of (a) a hydrocarbyl substituted acylating agent and (b) a reagent selected from the group consisting of a nitrogen-containing compound, a hydroxyl-containing compound and water which gives a reaction product selected from the group consisting of (1) a mono-amide / mono-acid or a metal-free diacid salt thereof, (2) a diacid or a diacid free salt metal thereof, and (3) a mono-ester / mono-acid or a metal-free mono-acid salt thereof. The reaction product comprises at least about 10 mole percent of acidic groups based on the total number of moles of reaction product.
    公开号:BE1023617B1
    申请号:E2011/0620
    申请日:2011-10-26
    公开日:2017-05-17
    发明作者:Xinggao Fang
    申请人:Afton Chemical Corporation；
    IPC主号:
    专利说明:

    ADDITIVE FOR DIESEL FUEL
    TECHNICAL AREA
    The invention relates to certain additives for diesel fuel and diesel fuels and diesel fuel additive concentrates which comprise the additive. In particular, the invention relates to methods for improving fuel economy and cleanliness of fuel injectors, filters and fuel supply systems for compression ignition engines.
    CONTEXT AND SUMMARY
    [0002] The indirect injection diesel engine has now almost exclusively been replaced on the market by more modern direct injection light diesel engines for reasons of fuel economy, performance and emission reduction. However, direct injection diesel engines are much more sophisticated than older indirect injection engines and require the maintenance of more accurate calibration to maintain their theoretical performance. Injectors, which are key components in engine performance, are vulnerable because their operation is likely to be disrupted by fouling due to deposits from fuel injection or combustion.
    [0003] Direct injection engines can also use a high-pressure common-rail supply circuit or a unitary injection system. Problems have recently been associated with the use of low sulfur and ultra low sulfur diesel fuels in these high pressure common rail fuel systems. "High pressure" refers to pressures in diesel fuel systems that are greater than or equal to 15,000 psi (greater than or equal to 1,000 bar). These problems are manifested by the presence of sediment in the batches of fuel additive, deposits in the internal injector and blockage of the injectors. Therefore, it was necessary to have fuel additives that are effective in reducing the amount of deposition in the feed circuits and / or that are effective in cleaning fouled feed circuits.
    In view of the needs described above and other needs, the embodiments of the invention provide an additive composition for diesel fuel, a fuel containing the fuel additive, a method for improving performance. of a diesel engine using the additive. The diesel fuel additive comprises a reaction product of (a) a hydrocarbyl substituted acylating agent and (b) a reagent selected from the group consisting of a nitrogen-containing compound, a hydroxyl-containing compound and water which gives a reaction product selected from the group consisting of (1) a mono-amide / mono-acid or a metal-free mono-acid salt thereof, (2) a diacid or a salt of metal-free diacid thereof, and (3) a mono-ester / mono-acid or a metal-free mono-acid salt thereof, the reaction product comprising at least about 10 mole percent of groups acid relative to the total number of moles of the reaction product.
    [0005] Another embodiment of the present invention provides a method for improving the performance of a diesel fuel engine containing 50 ppm by weight or less of sulfur, typically less than about 20 ppm sulfur by weight. relative to the total weight of the fuel. The process comprises combining a low sulfur middle distillate fuel with a fuel additive comprising a reaction product of (a) a hydrocarbyl substituted acylating agent and (b) a reagent selected from the group consisting of a nitrogen-containing compound, a hydroxyl-containing compound and water which provides a reaction product selected from the group consisting of (1) a mono-amide / mono-acid or a mono salt metal-free acid thereof, (2) a diacid or a metal-free diacid salt thereof, and (3) a mono-ester / mono-acid or a metal-free mono-acid salt thereof of these, the reaction product comprising at least about 10 mole percent acid groups based on the total moles of the reaction product. The fuel with an additive is burned in the engine, whereby the engine performance is improved with respect to engine performance in the absence of the fuel additive.
    Still another embodiment of the invention provides a low sulfur diesel fuel composition suitable for a high pressure compression ignition engine. The diesel fuel composition comprises a) a major amount of low sulfur diesel fuel, and b) a minor amount of additive to reduce fuel and fuel system deposits. The additive is a reaction product of (i) a hydrocarbyl substituted acylating agent and (ii) a reagent selected from the group consisting of a nitrogen-containing compound, a hydroxyl-containing compound and a water which gives a reaction product selected from the group consisting of (1) a mono- / mono-acid mono-amide or a metal-free mono-acid salt thereof, (2) a diacid or a diacid-free salt of metal thereof, and (3) a mono-ester / mono-acid or a metal-free mono-acid salt thereof, the reaction product comprising at least about 10 mole percent acid groups per unit relative to the total number of moles of the reaction product.
    Other embodiments provide a method of increasing the fuel economy of a vehicle, including burning the diesel fuel composition as described herein wherein said fuel economy increase is defined by the efficiency of the fuel economy. in power, and said power efficiency is greater than 50% as determined by the formula
    Efficiency = (DU-CU) / DU in which DU represents the percentage of power loss during a fouling phase without the additive, CU represents the percentage of power loss during a cleaning phase with the additive for fuel, and the power is measured in accordance with CEC test F98-08 DW10.
    [0008] In accordance with one or more embodiments of the invention, the additive for use in a diesel fuel can provide benefits that include, but are not limited to: a) maintaining the cleanliness of the fuel systems; fuel supply including injectors and fuel filters; (b) the ability to clean dirty or dirty fuel systems; (c) the contribution to doping or increased fuel savings; (d) the reduction of deposits in combustion systems; e) reduction of corrosion of the supply circuits; f) and improving the lubrication of the fuel system and the combustion chamber. The additives of the invention can provide beneficial effects similar to other middle distillate fuels, such as home heating oils, ship fuel and jet fuel.
    BRIEF DESCRIPTION OF THE DRAWING
    Figure 1 is a graphical illustration of the power loss over time for an additive according to the invention and a comparative additive in a diesel engine.
    DETAILED DESCRIPTION OF THE DISCLAIMED EMBODIMENTS
    Other features, embodiments and advantages thereof may be provided by the following detailed description of the embodiments of the invention. An important feature of the embodiments described herein is that the reaction product used as a fuel additive component contains less than about 90 mole percent of an imide and a substantially zero amount of diamide or diester components relative to the total number of moles of the reaction product as determined by Fourier transform infrared spectroscopy (SITF). For example, the reaction product may contain less than 70 mole percent of the imide and suitably from about 0 to about 60 mole percent imide based on the total moles of the reaction product.
    Another important feature of the embodiments described herein is that the reaction product contains at least about 10 mole percent acid groups based on the total number of moles of the reaction product. For example, the reaction product may contain from about 10 to about 20 mole percent or more of acidic groups. In another example, the reaction product may contain from about 20 to about 50 mole percent acid groups. In yet another example, the reaction product may contain about 100 mole percent acid groups.
    Although it is difficult to fully determine the components of the reaction product, for purposes of this invention, the reaction product is characterized by its major or major component prepared using the reagents. For example, depending on the reagent (b), each dicarboxylic acylating agent functional group of the reaction product may be primarily a diacid or a metal-free diacid salt thereof, a mono-amide / mono-acid or a metal-free salt thereof, or a mono-ester / mono-acid or a metal-free salt thereof as described in more detail below. In each case where the reaction product comprises an acidic or salt functional group, the acid or salt functional group may in fact be a mixture of acidic functional groups and salts. It will be appreciated that the reaction product may also comprise unreacted components and / or by-products which may be a major or minor part of the reaction product. However, with all reagents (b), the reaction product desirably contains at least one metal-free carboxylic acid group or a nitrogen-containing salt thereof.
    The first component used to prepare the reaction product is a hydrocarbyl substituted acylating agent. The molecular weight of the hydrocarbyl substituted acylating agent can be determined by exclusion-diffusion chromatography (EDC). The DAC separation process comprises column chromatography in which the stationary phase is a solvent-swellable heteroporous polymer network of a polystyrene gel whose permeability varies by several orders of magnitude. When the liquid phase (tetrahydrofuran) containing the polymer sample passes through the gel, the polymer molecules diffuse into all parts of the gel that do not provide a mechanical barrier. The smaller molecules "permeate" it more completely and spend more time in the column; the larger molecules "impregnate" it less and cross the column more quickly. The Mn and Mw values of the hydrocarbyl substituted acylating agent can be obtained by comparing the distribution data obtained by CED with a series of calibration standards of polymers of known molecular weight. The average molecular weight of the hydrocarbyl substituted acylating agent according to the embodiments of the invention can be determined by CED using a polystyrene standard.
    In the context of the invention, the term "hydrocarbyl group" or "hydrocarbyl" is used in its ordinary meaning, which is well known to those skilled in the art. Specifically, a hydrocarbyl group refers to a group having a carbon atom directly attached to the remainder of a molecule and having a predominantly hydrocarbon character. Examples of hydrocarbyl groups include: (1) hydrocarbon substituents, i.e., aliphatic (e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl), aromatic, aliphatic and alicyclic substituted aromatic, and cyclic substituents in which the ring is supplemented by another part of the molecule (for example, two substituents together form an alicyclic radical); (2) substituted hydrocarbon substituents, that is, substituents containing non-hydrocarbon groups which, in the context of the present description, do not modify the predominantly hydrocarbon substituent (e.g., halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso and sulfoxy); (3) hetero-substituents, that is, substituents which, although having a predominantly hydrocarbon character, in the context of the present specification, contain atoms other than carbon in a ring or chain other than those consisting of carbon atoms. The hetero atoms include sulfur, oxygen, nitrogen, and include substituents such as pyridyl, furyl, thienyl, and imidazolyl. In general, not more than two, or as a further example, no more than one non-hydrocarbon substituent is present for three carbon atoms in the hydrocarbyl group; in some embodiments, no non-hydrocarbon substituent is present in the hydrocarbyl group.
    In one aspect of the described embodiments, the hydrocarbyl substituent of the hydrocarbyl-substituted acylating agent may be derived from an alpha-olefin, an internal olefin, or a polyolefin having more than 12 carbon atoms. . Non-limiting examples in the case of alpha-olefins include 1-hexadecene, 1-tetradecene, 1-octadecene and mixtures of C14-C26 alpha-olefins. Polyolefins include, but are not limited to, highly branched polyethylene, copolymers of ethylene and alpha-olefin, polypropylene and butene polymers, for example isobutylene polymers. Suitable polyisobutenes for the present use include polyisobutene polyisobutylene or highly reactive polyisobutylene having a terminal vinylidene content of at least about 60%, e.g. from about 70% to about 90% and more. Suitable polyisobutenes can include those prepared using BF3 catalysts. The number average molecular weight of the hydrocarbyl substituent may vary over a wide range, for example from about 100 to about 5,000, for example from about 500 to about 5,000, as determined by CED as described above. above. A particularly useful additive contains a polyisobutenyl group of the hydrocarbyl substituted acylating agent having a number average molecular weight (Mn) in the range of about 350 to 2300 as determined by CED.
    The carboxylate component of the acylating agent may be chosen from a dicarboxylic acid or a glycolic acid or an anhydride thereof or glyoxal. For example, the carboxylate component may be a succinic acid or anhydride prepared from an acid or maleic anhydride. When the acylating agent is not a succinic acid or anhydride derivative, carboxylic reagents other than maleic anhydride may be employed such as fumaric acid, glutaric acid, glutaconic acid, malic acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid, ethylmaleic anhydride, dimethylmaleic anhydride, ethylmaleic acid, dimethylmaleic acid, hexyl maleic acid and the like, including acid halides and corresponding lower aliphatic esters. The molar ratio of maleic anhydride to hydrocarbyl component in the reaction mixture can vary widely. Therefore, the molar ratio can range from about 5: 1 to about 1: 5, for example from about 3: 1 to about 1: 3, and by way of further example, the dicarboxylic component can be used in a Stoichiometric excess to ensure that the reaction goes to completion. A particularly useful hydrocarbyl-substituted acylating agent may have a weight average molecular weight (Mw) distribution with a number average molecular weight (Mn) greater than 1.4 (Mw / Mn) in the reaction product. The unreacted dicarboxylic component can be removed by vacuum distillation.
    As used herein, the term "major amount" should be understood to mean an amount greater than or equal to 50% by weight, for example from about 80 to about 98% by weight based on the total weight of the composition. In addition, as used herein, the term "minor amount" should be understood to mean less than 50% by weight based on the total weight of the composition.
    The term "middle distillate fuel" as used herein may be, for example, a naphtha, kerosene or a diesel fuel composition. It may be heating oil, industrial diesel, drilling oil, automotive diesel fuel, distillate fuel for ships or kerosene fuel such as aviation fuel or kerosene of heating. This can in particular be a composition of diesel fuel. More particularly, a medium distillate fuel is a fuel that is suitable and / or adapted and / or adapted for use in an internal combustion engine; for example a fuel composition for automobiles, and / or adapted and / or designed to be used in a diesel engine (ignition compression) of a motor vehicle. Such a fuel consisting of a middle distillate may be an organic or synthetic derivative, for example a petroleum derivative or a diesel fuel derived by the Fischer-Tropsch process. A medium distillate fuel may have boiling points in the usual range for diesel of 125 or 150 to 400 or 550 ° C, depending on the quality and use. The average distillate fuel density can vary from 0.75 to 1.0 g / cm3, for example, from 0.8 to 0.86 g / cm3, at 15 ° C and have a measured cetane number. (ASTM D613) from 35 to 80, suitably from 40 to 75 or 70. The initial boiling point of a medium distillate fuel may suitably be in the range of 150 to 230 ° C and the fuel may have a final boiling point in the range of 290 to 400 ° C. The kinematic viscosity of the middle distillate fuel at 40 ° C (ASTM D445) can suitably range from 1.5 to 4.5 mm 2 / s (centistokes).
    [00019] The diesel fuels of the described embodiments can be applied to stationary diesel engines (for example, engines used in power generation plants, pumping stations, etc.) as well as to mobile diesel engines. (for example, engines used as generators of motive power in automobiles, trucks, graders, military vehicles, etc.).
    [00020] It should be noted that, as used in this specification and the related claims, the singular forms "a", "a", "the" and "the" include plural forms unless explicitly and unequivocally a given term. Thus, for example, the reference to "an antioxidant" includes two or more different antioxidants. As used herein, the term "understand" and its grammatical variants are intended to be nonlimiting, so that the enumeration of the elements of a list does not mean the exclusion of other similar elements that may be substituted or added to the items listed.
    As noted above, it has been unexpectedly found that reducing the amount of imide reaction product in the additive can provide significant advantages over certain low-carbon diesel fuels. sulfur, especially when used in diesel engines having a high pressure common rail injection system. In order to reduce the amount of imide formed in the reaction product, the amount of reagent reactive with the hydrocarbyl substituted acylating agent may be controlled so as not to exceed 1 equivalent per equivalent of hydrocarbyl-substituted acylating agent.
    In one embodiment, the reaction product used as an additive contains less than about 90 mole percent imide, for example, less than about 70 mole percent imide, and suitably from about 0 to about 60 mole percent imide. The reaction product may also be substantially free of diamide reaction products and diester reaction products. In order to obtain the above reaction product, the hydrocarbyl substituted acylating agent is reacted with a nitrogen-containing compound, a hydroxyl-containing compound, or water.
    The nitrogen-containing compound may be selected from an amine, a polyamine, ammonia, aminoguanidine, piperazine and piperazine derivatives, aminotriazole, morphine, Aminotetrazole, hydrazine, guanidine, aminopyrimidine and others. Any of the many amines, polyamines, and the like can be used in the preparation of the reaction product. Non-limiting examples of the amines include methylamine, 2-ethylhexylamine, n-dodecylamine, stearylamine, N, N-dimethylpropanediamine, N- (3-aminopropyl) morpholine, N-dodecylpropanediamine, N-aminopropyl-piperazine and others.
    Non-limiting examples of polyamines may include aminoguanidine bicarbonate (AGBC), ethylenediamine, diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (ΤΕΡΑ), pentaethylenehexamine (PEHA) and polyamines heavy. A heavy polyamine may comprise a mixture of polyalkylene polyamines having small amounts of lower polyamine oligomers such as ΤΕΡΑ and PEHA, but mainly oligomers having seven or more nitrogen atoms, two or more primary amines per molecule, and branches more developed than conventional polyamine mixtures. Additional nonlimiting examples of the polyamines that can be used to prepare the hydrocarbyl-substituted additive component are described in U.S. Patent No. 6,548,458, the invention of which is incorporated herein by reference in its entirety. In one embodiment of the invention, the polyamine may be selected from tetraethylenepentamine (ΤΕΡΑ). [00025] The compounds containing hydroxyl include, but are not limited to, ethanolamine, diethanolamine, triethanolamine, N-ethanol-ethylenediamine, C 1 -C 18 alcohols and the like.
    In one embodiment, the additive component may comprise the compounds corresponding to the following formula: (1)
    and ammonia or amino salts thereof, wherein R is a hydrocarbyl group having 10 or more atoms and R1 is an OH group, an alkoxy group, an amine, a polyamine or an alkoxyamine functional group, provided that R does not have more than 12 carbon atoms when R1 is OH. For example, when the polyisobutylene substituted maleic anhydride is reacted with methylpiperazine, the reaction product may contain a major portion of a compound of the formula: (2)
    wherein PIB is a polyisobutylene group. Reaction of polyisobutylene-substituted maleic anhydride with aminotetrazole may yield a compound of the formula:
    (3); the reaction with 2-hydroxylethylpyridine can give a compound of the formula:
    (4); the reaction with triethanolamine can give a compound corresponding to the formula:
    (5); and the reaction with water can give a compound of the formula: (6)
    The foregoing additive may be prepared with a molar ratio of (a) hydrocarbyl substituted acylating agent to (b) reactant in the reaction medium in the range of 10/1 to 1/10.
    The other reaction conditions are illustrated in the examples contained herein.
    When formulating the fuel containing the additive as described herein, the fuel may contain an amount of additive ranging from about 10 to about 10,000 ppm by weight per volume of fuel, such as about 80 ppm by weight at about 200 ppm by weight per volume of fuel. For example, in order to maintain the cleanliness of the fuel system and injectors, the fuel may contain from about 10 to about 100 ppm by weight per volume of fuel. However, from about 100 to about 200 ppm by weight per volume of fuel can be used to clean a dirty feed circuit in order to restore power in a relatively short period of time. In aspects where a carrier is employed to provide a composition containing the fuel additive, the additive compositions may contain, based on the active ingredients, a carrier amount ranging from about 10 mg to about 1000 mg of support per kg of fuel, for example from about 25 mg to about 700 mg of carrier per kg of fuel. The base of the active substances excludes the weight of the (i) unreacted components associated with the additives and remaining therein as produced and used, and (ii) the solvent (s), if any, used in the manufacture additives described either during or after their formation but before the addition of a carrier, if a carrier is used.
    The additive of the present invention may be added to a base fuel individually or in various sub-combinations. In some embodiments, the additive of the present invention can be added to a fuel simultaneously by using an additive concentrate, as this allows to take advantage of the mutual compatibility and practicality offered by the combination of substances when are in the form of an additive concentrate. In addition, the use of a concentrate can reduce the mixing time and reduce the risk of mixing errors.
    [00030] One or more additional optional additives may be present in the fuel compositions described herein. For example, the fuel compositions may contain antifoam agents, additional dispersants, detergents, antioxidants, heat stabilizers, carrier fluids, metal deactivators, dyes, labels, corrosion inhibitors, biocides, antistatic additives, friction reducing agents, friction modifiers, demulsifiers, emulsifiers, scavengers, de-icers, anti-knock agents, surfactants, cetane improvers, corrosion inhibitors, cold flow improvers, pour point depressants, solvents, demulsifiers, lubricity agents, extreme pressure agents, viscosity index improvers, swelling of joints, amine stabilizers, combustion improvers, dispersants, conductivity improvers, organic nitrate ignition accelerators, manganese tricarbonyl compounds, and mixtures thereof. In some aspects, the fuel additive compositions described herein may contain about 10% by weight or less, or in other aspects, about 5% by weight or less, based on the total weight of the additive or fuel composition, one or more of the additives described above. Also, the fuel compositions may contain adequate amounts of fuel blend components such as methanol, ethanol, dialkyl ethers and the like.
    In order to illustrate in more detail the features and advantages of the described embodiments, the following nonlimiting examples are provided. For the purposes of the following examples, the molecular weight of the additives was measured by exclusion-diffusion chromatography (EDC) with tetrahydrofuran (THF) as the solvent. Molecular weight polystyrene standards in the desired ranges were used as standards.
    Comparative Example 1 [00032] A fuel additive was produced by reacting polyisobutylene succinic anhydride (PIBSA) with a polyamine (PAM), in this case tetraethylenepentamine (ΤΕΡΑ) in a molar ratio PIBSA / PAM = 1 / 1. A modified procedure as described in US Pat. No. 5,752,989 was used to prepare the reaction product as follows: PIBSA (551 g) was diluted in 200 grams of Aromatic 150 solvent in a nitrogen atmosphere. The mixture was heated to 115 ° C. 112 grams of ΤΕΡΑ were then added via an addition funnel. The addition funnel was rinsed with an additional 50 grams of Aromatic 150 solvent. The reaction mixture was heated at 180 ° C for about 2 hours under a slow nitrogen sweep. The water was recovered in a Dean-Stark trap during the reaction. The product was obtained as a brownish oil. Fourier transform infrared spectroscopy (SITF) analysis showed a surface ratio of imide (1,701 cm-1) to amide (1,670 cm-1) of 22/1 in the reaction product.
    Comparative Example 2 [00033] An additive was prepared as described in Example 1, except that the ΤΕΡΑ was replaced with diethanolamine. SITF analysis showed a mixture of ester (1735 cm-1) and amide groups (1637 cm-1), and no trace of imide, carboxylic acid, or carboxylate functionality was observed in the reaction product.
    Comparative Example 3 [00034] An additive was prepared as described in Example 1, except that each mole of ΤΕΡΑ was replaced by 2 moles of 4-methylpiperazine.
    Comparative Example 4 [00035] An additive was prepared as described in Example 1. The reaction product was then reacted again with 1,8-naphthalic anhydride per mole of PIBSA in the reaction product. .
    Comparative Example 5 [00036] An additive was prepared as in Example 1, except that ΤΕΡΑ was replaced by aminoguanidine bicarbonate. The reaction product was then reacted again with 1 mole ΤΕΡΑ per mole of PIBSA in the reaction product.
    Comparative Example 6 An additive was prepared as described in Example 1, except that PIBSA was replaced by alkenyl succinic anhydride wherein the alkylenyl group has an average of 16 atoms of carbon, and that the ΤΕΡΑ has been replaced by polyetherdiamine.
    Comparative Example 7 A mixture was prepared with the reaction product of Example 1 and a bisaminotriazole which was prepared according to the general procedure of Example 1 in US Patent No. 5,174,915, except for the fact that polyisobutylene (PIB) of molecular weight 950 was used.
    Example 8 [00039] An additive was prepared as in Example 1, set
    On the other hand, the temperature was not raised to 180 ° C during the reaction and no additional effort was made to remove the water during the reaction. The reaction product was neutralized with a tertiary amine in a 1/1 molar ratio (PIBSA / tertiary amine). SITF analysis showed that the surface ratio of imide to amide was about 1/1.
    Example 9 [00040] An additive was prepared as in Example 1, except that ΤΕΡΑ was replaced by aminoguanidine bicarbonate.
    Example 10 [00041] An additive was prepared as described in Example 1, except that each mole of ΤΕΡΑ was replaced by 1.5 moles of water and the reaction was carried out below of 80 ° C. The reaction mixture was filtered through a filter aid.
    Example 11 [00042] An additive was prepared as described in Example 10, except that PIBSA was replaced by an alkenyl succinic anhydride (ASA) having about 20 to 24 carbon atoms in each case. the alkenyl group.
    Example 12 [00043] An additive was prepared as in Example 1, except that ΤΕΡΑ was replaced by 5-aminotetrazole.
    Example 13 [00044] An additive was prepared as described in Example 11, except that the water was replaced by triethanolamine. The molar ratio of ASA to triethanolamine in the reaction mixture was 2 to 1.
    Example 14 [00045] An additive was prepared according to Example 3, except that the molar ratio of PIBSA to 4-methylpiperazine used in the reaction mixture was a molar ratio of 1 to 1. SITF analysis showed the presence of acid (1716 cm-1) and amide (1646 cm-1) groups in the reaction product.
    Example 15 [00046] An additive was prepared according to Example 14 except that 4-methylpiperazine was replaced with 2-hydroxyethylpyridine.
    Example 16 [00047] An additive was prepared according to Example 1, except that the reaction product was exposed to moisture vapor for a prolonged period. SITF showed a surface ratio of imide (1698 cm-1) to amide (1648 cm-1) 1/10 in the reaction product.
    In the following examples, the effect that additives prepared according to the methods of Examples 8 to 16 had on diesel fuel for high pressure common rail diesel fuel systems was evaluated. A DW10 test developed by the Coordinating European Council (CEC) has been used to illustrate the tendency of fuels to cause fouling of fuel injectors and has also been used to illustrate the ability of certain fuel additives to prevent or control these deposits. A dynamometer test stand for the engine was used for the installation of the Peugeot DW10 diesel engine to perform CEC F-98-08 tests. The engine was a 2.0-liter engine equipped with four cylinders. Each combustion chamber had four valves and the fuel injectors were Euro VI Piezo DI injectors.
    [00049] The central protocol procedure was to feed the engine with a fuel containing 1 ppm of zinc neodecanoate during an 8 hour cycle and to allow the engine to stand (engine off) for a prescribed period of time. The previous sequence was repeated four times. At the end of each hour, a measurement of engine power was taken while the engine was operating at the given conditions. The fouling tendency of the fuel injectors was characterized by a nominal power difference observed between the beginning and the end of the test cycle.
    The preparation of the test consisted in particular of eliminating from the engine the fuel of the preceding test before the withdrawal of the injectors. The test injectors were inspected, cleaned and reinstalled in the engine. If new injectors were selected, the new injectors were subjected to a 16-hour break-in cycle. Then, the engine was started using the program of the desired test cycle. Once the engine was warmed up, power was measured at 4,000 rpm and at full load to verify full power restoration after injector cleaning. If the power measurements were within specification, the test cycle was started. The following Table 1 illustrates the carbonization cycle DW10 that was used to evaluate the fuel additives according to the invention.
    Table 1 - One hour representation of the DW10 carbonization cycle.
    Example 17 [00051] The carbonization tests of the diesel engine injectors were carried out in general accordance with the Peugeot DW10 engine according to CEC protocol F-98-08 of Table 1, except that the engines had not been used. only during an 8-hour cycle, unless otherwise specified. The engine was powered with diesel fuel (PC10) with zinc neodecanoate without additives to establish a baseline. In each of the Comparative Examples, Analyzes 1-7, the additive was used at a processing speed of 50 ppm by weight per volume of fuel. In each of the examples of the invention, Analyzes 8 to 15, the additive was used at a processing speed of 50 ppm by weight per volume of fuel. The loss of power is an indication of the fouling of the injectors. Ideally, in a cleanliness test, the decrease in power should be zero. Negative numbers indicate a power loss and positive numbers indicate a power increase. Table 2 illustrates the power variations for the comparative examples and Table 3 illustrates the power variations for the examples according to the embodiments of the invention.
    Table 2
    Table 3
    As indicated by the substantially low power loss and power increase in Analyzes 8 to 15, the additives prepared according to the described embodiments are substantially more efficient in maintaining the cleanliness of the feed circuits than the additives. Comparisons of Analyzes 1-7. Figure 1 illustrates the% change in rated power over a 16-hour test period for Analysis 4 (A) and Analysis 9 (B) versus the ideal power loss. nothing.
    Example 18 [00053] In the following examples, the ability of the additives to clean a dirty feed circuit was evaluated according to the protocol of the test of Example 17. Unless indicated, the comparative examples were obtained by running the engine without additive for 16 hours and then running the engine with the additive for 16 hours and determining the percentage of improvement in power as a result of cleaning the engine with the additive. In the examples of the invention, the engine ran without additive for 8 hours and then for 8 hours for cleaning, unless otherwise indicated. The percentage power yield was determined by the following formula
    Efficiency = (DU-CU) / DU in which DU represents the percentage of power loss during a fouling phase without the additive, CU represents the percentage of power loss during a cleaning phase with the additive for fuel, and the power is measured in accordance with CEC test F98-08 DW10. The comparative examples are illustrated in Table 4 and the examples of the invention are illustrated in Table 5.
    Table 4
    Table 5
    As indicated in the preceding examples, Analyzes 19 to 22, the reaction products of the additives of the invention produced a significant increase in power compared with the comparative examples of Analyzes 16 to 18.
    In the context of this specification and the related claims, unless otherwise indicated, all the numbers expressing quantities, percentages or proportions, and the other numerical values used in the specification and the claims, must be understood as being modified, in any case, by the word "about". Therefore, unless otherwise indicated, the numerical parameters indicated in the following specification and the related claims are approximations which may vary depending on the desired properties sought by the present invention. In any event, and without attempting to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter must at least be interpreted in light of the number of significant digits indicated and by applying classical rounding.
    Although particular embodiments have been described, substantial alternatives, modifications, variations, improvements and equivalents that are not or which may not be foreseen to date may be implemented by the applicants or the skilled person. Accordingly, the related claims as filed and as amended may be intended to encompass all of these alternatives, modifications, variations, improvements and substantial equivalents.
    权利要求:
    Claims (19)
    [1]
    CLAIMS:
    A method for improving the performance of a diesel fuel engine containing 50 ppm by weight or less of sulfur, said process comprising: combining a fuel consisting of a low sulfur middle distillate with a fuel. fuel additive comprising a reaction product of {a} a hydrocarbyl substituted acylating agent and (b) a reagent selected from the group consisting of: ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, ammonia, bicarbonate aminoguanidine, guanidine, piperazine, methyl piperazine, aminopyrimidine, aminotriazole and aminotetrazole, alkanolamines, N-ethanol-ethylenediamine, hydroxyethyl pyridine, water, and mixtures thereof, which gives at least 10 mol% of a selected reaction product in the group consisting of {1} a mono-amide / mono-acid or a metal-free mono-acid salt thereof, and (2) a mono-e ster / mono-acid or a metal-free mono-acid salt thereof, the reaction product comprising at least 10 mole percent of acidic groups or salts containing nitrogen relative to the total moles of the reaction product; and burning fuel having an additive in the engine, whereby the engine performance is improved with respect to engine performance in the absence of the fuel additive.
    [2]
    The process according to claim 1, wherein the compound (b) is selected from the group consisting of ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, ammonia, aminoguanidine bicarbonate, piperazine, roethyl piperazine, aminopyridine, aminotriazole and aminotetrazole.
    [3]
    3. The process according to claim 1, wherein the alkanolamine is selected from alkanolamine C2 & C3.
    [4]
    The process of claim 1, wherein the hydrocarbyl substituted acylating agent is selected from the group consisting of hydrocarbyl substituted malonic anhydride, hydrocarbyl substituted succinic anhydride and hydrocarbyl substituted glutaric anhydride.
    [5]
    The process of claim 1 wherein the hydrocarbyl substituted acylating agent comprises polyisobutenyl substituted succinic anhydride.
    [6]
    The process according to claim 1, wherein the hydrocarbyl substituted acylating agent comprises a C14 alkenyl substituted succinic anhydride.
    [7]
    The process of claim 1, wherein the reaction product is derived from a maximum of about one equivalent of reagent (b) by hydrocarbyl-substituted acylating agent.
    [8]
    8. The process according to claim 1, wherein the reaction product contains from 0 to less than about 60% by weight of an imide based on the total weight of reaction product.
    [9]
    9. A low sulfur diesel fuel composition suitable for a high pressure compression ignition engine, comprising: a) a major amount of low sulfur diesel fuel, and b) a minor amount of an additive for reducing the deposits in the injection and fuel system, the additive comprising: a reaction product of (i) a hydrocarbyl substituted acylating agent and (ii) a reagent selected from the group consisting of: ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, ammonia, aminoguanidine bicarbonate, guanidine, piperazine, methyl piperazine, aminopyrimidine, aminotriazole and aminotetrazole, alkanolamines, H-ethanol-ethylenediamine, hydroxyethyl pyridine, water, and mixtures thereof, which gives at least 10 mol% of a reaction product selected from the group consisting of (1) a mono-amide / mono-acid or a salt of m metal-free ono-acid thereof; and (2) a mono-ester / mono-acid or a metal-free mono-acid salt thereof, wherein the reaction product comprises at least 10 percent in moles of acid groups or salts containing nitrogen relative to the total number of moles of the reaction product.
    [10]
    The diesel fuel composition according to claim 9, wherein the compound (ii) is selected from the group consisting of ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene * hexamine, ammonia, bicarbonate and the like. aminoguanidine, piperazine, methyl piperazine, aminopyrimidine, aminotriazole and aminotetrazole.
    [11]
    The composition of claim 9, wherein the compound (ii) is an alkanolamine selected from C2 to C3 alkanolamines.
    [12]
    The diesel fuel composition of claim 19, wherein the reaction product is derived from a maximum of about one equivalent of reagent (b) by hydrocarbyl substituted acylating agent.
    [13]
    The diesel fuel composition of claim 9, wherein the reaction product contains less than about 60 percent by weight of an imide based on the total weight of the reaction product.
    [14]
    The diesel fuel composition according to claim 9, wherein the reaction product comprises at least one compound of formula (1):

    (1) and ammonia or amino salts thereof, wherein R is a hydrocarbyl group having 10 or more carbon atoms and R * is an alkoxy group, an amine, a polyamine or an alkoxyamine moiety .
    [15]
    The diesel fuel composition according to claim 14, wherein the compound of formula (1) is selected from the group consisting of:


    (3); .

    (4); <55;

    formulas in which PIB is a polyisobutylene group.
    [16]
    The composition of claim 9, wherein the hydrocarbyl substituted acylating agent is selected from the group consisting of hydrocarbyl substituted malonic anhydride, hydrocarbyl substituted succinic anhydride and hydrocarbyl substituted glutaric anhydride.
    [17]
    The composition of claim 9 wherein the hydrocarbyl substituted acylating agent is polyisobutenyl substituted succinic anhydride.
    [18]
    A method of increasing the fuel economy of a vehicle, comprising burning the diesel fuel composition according to claim 9, wherein said increasing fuel economy is defined by the power efficiency, and said fuel efficiency power is greater than 50% as determined by the power efficiency formula - (DU-CU) / DU in which DU represents the percentage of power loss during a fouling phase without the additive, CU represents the percentage of loss during a cleaning phase with the fuel additive, and the power is measured according to the F98-08 DW10 test of the Coordinating European Council (CEC).
    [19]
    19. The method of claim 18 wherein the power efficiency is greater than about 50%.
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    同族专利:
    公开号 | 公开日
    US20120102826A1|2012-05-03|
    US20140123546A1|2014-05-08|
    GB2487619A|2012-08-01|
    GB201118861D0|2011-12-14|
    GB2487619B|2014-05-14|
    US8668749B2|2014-03-11|
    US9102891B2|2015-08-11|
    CN102559303A|2012-07-11|
    SG180152A1|2012-05-30|
    CN102559303B|2015-01-14|
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    法律状态:
    优先权:
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